Well-defined complex macromolecular architectures by anionic polymerization of styrenic single and double homo/miktoarm star-tailed macromonomers

Styrenic single and double star-tailed macromonomers were synthesized by selective reaction of living homo/miktoarm stars with the chlorosilane groups of 4-(chlorodimethylsilyl)- and 4-(dichloromethylsilyl)styrene, respectively. The in situ anionic homopolymerization of macromonomers with sec-BuLi and copolymerization with butadiene and styrene, led to single/double homo/miktoarm star-tailed molecular brushes and combs, as well as a block copolymer consisting of a linear polystyrene chain and a double miktoarm (PBd/PS) star-tailed brush-like block. Molecular characterization by size exclusion chromatography, size exclusion chromatography/two-angle laser light scattering, and NMR spectroscopy, revealed the high molecular/compositional homogeneity of all intermediate and final products. These are only a few examples of the plethora of complex architectures possible using the above macromonomers.